Transformation and biodegradation of 1,2,3-trichloropropane (TCP)

PURPOSE: 1,2,3-Trichloropropane (TCP) is a persistent groundwater pollutant and a suspected human carcinogen. It is also is an industrial chemical waste that has been formed in large amounts during epichlorohydrin manufacture. In view of the spread of TCP via groundwater and its toxicity, there is a need for cheap and efficient technologies for the cleanup of TCP-contaminated sites. In situ or on-site bioremediation of TCP is an option if biodegradation can be achieved and stimulated. This paper presents an overview of methods for the remediation of TCP-contaminated water with an emphasis on the possibilities of biodegradation. CONCLUSIONS: Although TCP is a xenobiotic chlorinated compound of high chemical stability, a number of abiotic and biotic conversions have been demonstrated, including abiotic oxidative conversion in the presence of a strong oxidant and reductive conversion by zero-valent zinc. Biotransformations that have been observed include reductive dechlorination, monooxygenase-mediated cometabolism, and enzymatic hydrolysis. No natural organisms are known that can use TCP as a carbon source for growth under aerobic conditions, but anaerobically TCP may serve as electron acceptor. The application of biodegradation is hindered by low degradation rates and incomplete mineralization. Protein engineering and genetic modification can be used to obtain microorganisms with enhanced TCP degradation potential.     

Allocating Remedial Costs at Superfund Sites with Commingled Groundwater Contaminant Plumes

Remedial efforts at Superfund sites across the country focus on groundwater contaminant plumes that have been produced by contributions from multiple parties. Allocating cleanup costs between the parties in a fair and equitable manner can be a problem of substantial complexity. Considerable time and money may be spent determining the amount of contamination attributable to each party in order to apportion liability. Contaminant plumes that have evolved over long periods of time may affect large volumes of groundwater and require extensive remediation. Pump and treat remedial costs are driven by both the volume of water extracted and the mass of contaminants removed. Allocation methods based solely on the mass of contaminants contributed by each party are inadequate in this setting since they do not account for both components of the remedial costs. This paper presents an approach for equitably allocating remedial costs when addressing overlapping or commingled groundwater plumes. The method accounts for the major elements driving the costs of remediating dispersed contaminant plumes.     

Allocating Remedial Costs at Superfund Sites with Commingled Groundwater Contaminant Plumes

Remedial efforts at Superfund sites across the country focus on groundwater contaminant plumes that have been produced by contributions from multiple parties. Allocating cleanup costs between the parties in a fair and equitable manner can be a problem of substantial complexity. Considerable time and money may be spent determining the amount of contamination attributable to each party in order to apportion liability. Contaminant plumes that have evolved over long periods of time may affect large volumes of groundwater and require extensive remediation. Pump and treat remedial costs are driven by both the volume of water extracted and the mass of contaminants removed. Allocation methods based solely on the mass of contaminants contributed by each party are inadequate in this setting since they do not account for both components of the remedial costs. This paper presents an approach for equitably allocating remedial costs when addressing overlapping or commingled groundwater plumes. The method accounts for the major elements driving the costs of remediating dispersed contaminant plumes.     

Estimating contaminant-flushing rates for heterogeneous aquifers

Groundwater remediation evaluations typically include cleanup time projections. Current batch flushing-rate equations and analytical models often used to estimate groundwater cleanup rates typically underestimate cleanup times, with a major factor the flawed assumption of aquifer homogeneity. Numerical modelling of groundwater flow and contaminant transport is a time-intensive and costly alternative. An analytical modelling approach has been developed to quickly and cost effectively approximate realistic contaminant cleanup rates, factoring aquifer heterogeneity into the process. The mathematical relationships predict residual dissolved concentrations and average pumped concentrations over time, and also the time required to meet a concentration standard.     

污染土壤及地下水修复的PRB技术及展望

PRB技术是一类就地修复污染土壤及地下水的新型技术 ,主要由注入井、浸提井和监测井3部分所组成。污染地区的水文地质学研究 ,是实施该技术的关键 ;化学活性物质的筛选、注入的部位、浓度、速率以及是否均匀分布 ,是该技术是否有效的关键要素。胶态零价铁PRB技术 ,被证明是一项修复由卤代烃、卤代芳烃和有机氯农药以及一些有毒金属 (如铬、硒、铀、砷和锝等 )引起的土壤及地下水污染的有效技术。尽管这些技术存在一定的弊病 ,但与传统的处理方法相比 ,其技术上的优势是十分明显的。可以预料 ,这一技术在我国有良好的应用前景     

Characterization and optimization of long-term controlled release system for groundwater remediation: a generalized modeling approach

A well-based reactive barrier system using controlled-release KMnO4 has been recently developed as a long-term in situ treatment option for plumes of dense and non-aqueous phase liquids in groundwater. In order to take advantage of the merits of controlled release systems (CRS) in environmental remediation, the release behavior needs to be optimized for the hydrologic and environmental conditions of target treatment zone. Where release systems are expected to be operated over long times, like for the reactive barriers, it may only be practical to describe the long-term behavior numerically. We developed a numerical model capable of describing release characteristics associated with variable forms and structures of long-term CRS. Sensitivity analyses and illustrative simulations showed that the release kinetics and durations would be constrained by changes in agent solubility, bulk diffusion coefficients, or structures of the release devices. The generality of the numerical model was demonstrated through simulations for CRS with monolithic and double-layered matrices. The generalized model was then used for actual design and analyses of an encapsulated-matrix CRS, which can yield constant release kinetics for several years. A well-based reactive barrier system (4.05 x 10(3)m3) using the encapsulated-matrix CRS can release approximately 1.65 kg of active agent (here MnO4(-)) daily over the next 6.6 yr, creating prolonged reaction zone in the subsurface. The generalized model-based, target-specific approach using the long-term CRS could provide practical tool for improving the efficacy of advanced in situ remediation schemes such as in situ chemical oxidation, bioremediation, or in situ redox manipulation. Development of techniques for adjusting the bulk diffusion coefficients of the release matrices and facilitating the lateral spreading of the released agent is warranted.     

An evaluation of the role of risk-based decision-making in a former manufactured gas plant site remediation

Environmental remediation decisions are driven by the need to minimize human health and ecological risks posed by environmental releases. The Risk Assessment Guidance for Superfund Sites enunciates the principles of exposure and risk assessment that are to be used for reaching remediation decisions for sites under Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). Experience with remediation management under CERCLA has led to recognition of some crucial infirmities in the processes for managing remediation: cleanup management policies are ad hoc in character, mandates and practices are strongly conservative, and contaminant risk management occurs in an artificially narrow context. The purpose of this case study is to show how a policy of risk-based decision-making was used to avoid customary pitfalls in site remediation. This case study describes the risk-based decision-making process in a remedial action program at a former manufactured gas plant site that successfully achieved timely and effective cleanup. The remediation process operated outside the confines of the CERCLA process under an administrative consent order between the utility and the New Jersey Department of Environmental Protection. A residential use end state was negotiated as part of this agreement. The attendant uncertainties, complications, and unexpected contingencies were overcome by using the likely exposures associated with the desired end state to structure all of the remediation management decisions and by collecting site-specific information from the very outset to obtain a detailed and realistic characterization of human health risks that needed to be mitigated. The lessons from this case study are generalizable to more complicated remediation cases, when supported by correspondingly sophisticated technical approaches.     

土壤、地下水中有机污染物的就地处置

有机化合物对土壤、地下水的污染已引起世界各国的普遍关注.地层介质中的有机物主要以自由态、挥发态、溶解态和固态4种形态存在.有机污染物的自然降解能力较差,如不进行人工清除,在自然环境中它们可能存留长达几十年之久,对土壤、地下水资源构成长期的威胁.传统的开挖处理技术不仅费用昂贵,而且当贮油设施的地表被利用时则无法进行开挖处理(如有建筑物等).近年来,以地下冲洗法、土壤抽水法和地下水曝气法为代表的有机污染物就地处置技术得到了迅速的发展.本文对这3种技术进行概要的介绍,总结指出决定这些技术可能性的主要因素是地层介质的通透能力,有机物的挥发、溶解能力及其可生物降解能力,并列出目前的主要有机污染物挥发、溶解及生物降解能力的相对强弱作为制定具体处置技术的参考指标.     

Effects of remediation train sequence on decontamination of heavy metal-contaminated soil containing mercury

When a contaminated site contains pollutants including both nonvolatile metals and Hg, one single remediation technology may not satisfactorily remove all contaminants. Therefore, in this study, chemical extraction and thermal treatment were combined as a remediation train to remove heavy metals, including Hg, from contaminated soil. A 0.2 M solution of ethylenediamine tetraacetic acid (EDTA) was shown to be the most effective reagent for extraction of considerable amounts of Cu, Pb, and Zn (>50%). Hg removal was ineffective using 0.2 M EDTA, but thermogravimetric analysis suggested that heating to 550°C with a heating rate of 5°C/min for a duration of 1 hr appeared to be an effective approach for Hg removal. With the employment of thermal treatment, up to 99% of Hg could be removed. However, executing thermal treatment prior to chemical extraction reduced the effectiveness of the subsequent EDTA extraction because nonvolatile heavy metals were immobilized in soil aggregates after the 550°C treatment. The remediation train of chemical extraction followed by thermal treatment appears to remediate soils that have been contaminated by many nonvolatile heavy metals and Hg.

ImplicationsA remediation train conjoining two or more techniques has been initialized to remove multiple metals. Better understandings of the impacts of treatment sequences, namely, which technique should be employed first on the soil properties and the decontamination efficiency, are in high demand. This study provides a strategy to remove multiple heavy metals including Hg from a contaminated soil. The interactions between thermal treatment and chemical extraction on repartitioning of heavy metals was revealed. The obtained results could offer an integrating strategy to remediate the soil contaminated with both heavy metals and volatile contaminants.     

Characterisation of microbial activity in the framework of natural attenuation without groundwater monitoring wells?: a new Direct-Push probe

At many contaminated field sites in Europe, monitored natural attenuation is a feasible site remediation option. Natural attenuation includes several processes but only the microbial degradation leads to real contaminant removal and very few methods are accepted by the authorities providing real evidence of microbial contaminant degradation activity. One of those methods is the recently developed in situ microcosm approach (BACTRAP®). These in situ microcosms consist of perforated stainless steel cages or PTFE tubes filled with an activated carbon matrix that is amended with ¹³C-labelled contaminants; the microcosms are then exposed within groundwater monitoring wells. Based on this approach, natural attenuation was accepted by authorities as a site remediation option for the BTEX-polluted site Zeitz in Germany. Currently, the in situ microcosms are restricted to the use inside groundwater monitoring wells at the level of the aquifer. The (classical) system therefore is only applicable on field sites with a network of monitoring wells, and only microbial activity inside the monitoring wells at the level of the aquifer can be assessed. In order to overcome these limitations, a new Direct-Push BACTRAP probe was developed on the basis of the Geoprobe® equipment. With respect to the mechanical boundary conditions of the DP technique, these new probes were constructed in a rugged and segmented manner and are adaptable to various sampling concepts. With this new probe, the approach can be extended to field sites without existing monitoring wells, and microbial activity was demonstrated to be measureable even under very dry conditions inside the vadose zone above the aquifer. In a field test, classical and Direct-Push BACTRAPs were applied in the BTEX-contaminated aquifer at the ModelPROBE reference site Zeitz (Germany). Both types of BACTRAPs were incubated in the centre and at the fringe of the BTEX plume. Analysis of phospholipid fatty acid (PLFA) patterns showed that the bacterial communities on DP-BACTRAPs were more similar to the soil than those found on classical BACTRAPs. During microbial degradation of the ¹³C-labelled substrate on the carrier material of the microcosms, the label was only slightly incorporated into bacterial biomass, as determined by PLFA analysis. This provides clear indication for decreased in situ natural attenuation potential in comparison to earlier sampling campaigns, which is presumably caused by a large-scale source remediation measure in the meantime. In conclusion, Direct-Push-based BACTRAPs offer a promising way to monitor natural attenuation or remediation success at field sites which are currently inaccessible by the technique due to the lack of monitoring wells or due to a main contamination present within the vadose zone.     

原位化学氧化法在土壤和地下水修复中的研究进展

综述了原位化学氧化法修复污染土壤及地下水的最新进展 ,着重介绍了几种氧化剂 ,如二氧化氯、双氧水及Fenton试剂、高锰酸钾和臭氧在土壤修复中的应用、不足及改进 ,并对化学氧化修复技术的发展前景进行了展望     

Pulsed pumping process optimization using a potential flow model

A computational model is applied to the optimization of pulsed pumping systems for efficient in situ remediation of groundwater contaminants. In the pulsed pumping mode of operation, periodic rather than continuous pumping is used. During the pump-off or trapping phase, natural gradient flow transports contaminated groundwater into a treatment zone surrounding a line of injection and extraction wells that transect the contaminant plume. Prior to breakthrough of the contaminated water from the treatment zone, the wells are activated and the pump-on or treatment phase ensues, wherein extracted water is augmented to stimulate pollutant degradation and recirculated for a sufficient period of time to achieve mandated levels of contaminant removal. An important design consideration in pulsed pumping groundwater remediation systems is the pumping schedule adopted to best minimize operational costs for the well grid while still satisfying treatment requirements. Using an analytic two-dimensional potential flow model, optimal pumping frequencies and pumping event durations have been investigated for a set of model aquifer-well systems with different well spacings and well-line lengths, and varying aquifer physical properties. The results for homogeneous systems with greater than five wells and moderate to high pumping rates are reduced to a single, dimensionless correlation. Results for heterogeneous systems are presented graphically in terms of dimensionless parameters to serve as an efficient tool for initial design and selection of the pumping regimen best suited for pulsed pumping operation for a particular well configuration and extraction rate. In the absence of significant retardation or degradation during the pump-off phase, average pumping rates for pulsed operation were found to be greater than the continuous pumping rate required to prevent contaminant breakthrough.     

Options for cleanup and disposal of pesticide wastes generated on a small‐scale

Abstract

Many processes have been investigated to dispose of obsolete pesticide stocks and clean up wastewater and contaminated soil. The processes vary in their stages of development and commercial utility. With the exception of incineration, no single process may be amenable to all pesticide waste. Thus, any chosen process must consider first the chemical constituents needing remediation, their concentration, and desired or regulated cleanup objectives. Incineration seems too impractical and expensive to clean up routinely generated wastewater and contaminated soil, but it may currently be the only practical option for obsolete stocks . Practical remediation processes for wastewater and contaminated soil produced by small waste generators are discussed. Cleanup should be viewed as an integration of physical, chemical, and biological technologies.     

Solvent extraction and tandem dechlorination for decontamination of soil

The United States Environmental Protection Agency (US EPA) guidelines allow removal of polychlorinated biphenyls (PCBs) from soils via solvent extraction. This option holds promise for removal of other recalcitrant organic contaminants as well. A study was undertaken to evaluate the effectiveness of solvent extraction with two tandem degradation techniques. The degradation techniques were chemical dehalogenation with immobilized reagents and gamma-ray irradiation. The integrated approach was evaluated with contaminated soils from wood treatment and electric power substation sites. Evaluations were carried out on a bench scale in the laboratory and on a semi-pilot scale at a contaminated site. Binary solvent mixture of alkanes and alcohols yielded the highest extraction efficiencies. Extraction efficiencies in excess of 90% were obtained for PCBs, polychlorinated dibenzo-p-dioxins (PCDDs) and polynuclear aromatic hydrocarbons (PAHs). Extracted PCBs were rapidly degraded through chemical dehalogenation or with high doses of the gamma-ray irradiation. The residual organics in the solvent mixture were removed with activated carbon, and the solvent was recycled for subsequent soil extractions. Contaminants adsorbed on the activated carbon were destroyed with a counter flow oxidation process.     

原位热处理技术修复重质非水相液体污染场地研究进展

重质非水相液体(DNAPLs)是土壤及地下水中广泛存在的有机污染物,原位热处理技术是目前修复受DNAPLs污染土壤及地下水的最具潜力的技术之一。综述了国内外常用原位热处理技术的基本原理及其影响因素,介绍了相关现场应用实例,并展望了该技术未来的应用前景和发展趋势,以期为中国污染土壤及地下水的原位修复提供有益借鉴。     

Biochar- and phosphate-induced immobilization of heavy metals in contaminated soil and water: implication on simultaneous remediation of contaminated soil and groundwater

Long-term wastewater irrigation or solid waste disposal has resulted in the heavy metal contamination in both soil and groundwater. It is often separately implemented for remediation of contaminated soil or groundwater at a specific site. The main objective of this study was to demonstrate the hypothesis of simultaneous remediation of both heavy metal contaminated soil and groundwater by integrating the chemical immobilization and pump-and-treat methods. To accomplish the objective, three experiments were conducted, i.e., an incubation experiment was first conducted to determine how dairy-manure-derived biochar and phosphate rock tailing induced immobilization of Cd in the Cd-contaminated soils; second, a batch sorption experiment was carried out to determine whether the pre-amended contaminated soil still had the ability to retain Pb, Zn and Cd from aqueous solution. BCR sequential extraction as well as XRD and SEM analysis were conducted to explore the possible retention mechanism; and last, a laboratory-scale model test was undertaken by leaching the Pb, Zn, and Cd contaminated groundwater through the pre-amended contaminated soils to demonstrate how the heavy metals in both contaminated soil and groundwater were simultaneously retained and immobilized. The incubation experiment showed that the phosphate biochar were effective in immobilizing soil Cd with Cd concentration in TCLP (toxicity characteristics leaching procedure) extract reduced by 19.6 % and 13.7 %, respectively. The batch sorption experiment revealed that the pre-amended soil still had ability to retain Pb, Zn, and Cd from aqueous solution. The phosphate-induced metal retention was mainly due to the metal–phosphate precipitation, while both sorption and precipitation were responsible for the metal stabilization in the biochar amendment. The laboratory-scale test demonstrated that the soil amended with phosphate removed groundwater Pb, Zn, and Cd by 96.4 %, 44.6 %, and 49.2 %, respectively, and the soil amended with biochar removed groundwater Pb, Zn, and Cd by 97.4 %, 53.4 %, and 54.5 %, respectively. Meanwhile, the metals from both groundwater and soil itself were immobilized with the amendments, with the leachability of the three metals in the CaCl₂ and TCLP extracts being reduced by up to 98.1 % and 62.7 %, respectively. Our results indicate that the integrated chemical immobilization and pump-and-treat method developed in this study provides a novel way for simultaneous remediation of both metal-contaminated soil and groundwater.     

Assessing performance and closure for soil vapor extraction: integrating vapor discharge and impact to groundwater quality

Soil vapor extraction (SVE) is typically effective for removal of volatile contaminants from higher-permeability portions of the vadose zone. However, contamination in lower-permeability zones can persist due to mass transfer processes that limit the removal effectiveness. After SVE has been operated for a period of time and the remaining contamination is primarily located in lower-permeability zones, the remedy performance needs to be evaluated to determine whether the SVE system should be optimized, terminated, or transitioned to another technology to replace or augment SVE. Numerical modeling of vapor-phase contaminant transport was used to investigate the correlation between measured vapor-phase mass discharge, MF(r), from a persistent, vadose-zone contaminant source and the resulting groundwater contaminant concentrations. This relationship was shown to be linear, and was used to directly assess SVE remediation progress over time and to determine the level of remediation in the vadose zone necessary to protect groundwater. Although site properties and source characteristics must be specified to establish a unique relation between MF(r) and the groundwater contaminant concentration, this correlation provides insight into SVE performance and support for decisions to optimize or terminate the SVE operation or to transition to another type of treatment.     

Protecting off-site populations and site workers from vapor discharges during shallow soil mixing at the North Carolina State University National Priorities List Site

Although vapor monitoring is generally a component of remedial action activities, most sites do not have routine gaseous releases or vapor clouds erupting from the soil during implementation of the cleanup process (or during cleanup of the site). At the North Carolina State University Lot 86 National Priorities List Site, over 8410 m3 (11,000 yd3) of chemical waste was disposed at the Site, including organic solvents and shock-sensitive and air- and water-reactive compounds. During the Remedial Action, it was imperative to protect site workers and off-site populations from potential inhalation exposures. Engineering controls were incorporated into the shallow soil mixing process to limit the release of gaseous compounds. To quantify potential exposures to on-site and off-site receptors, modeling was conducted to evaluate potential exposure routes and migration pathways. To demonstrate acceptable levels of airborne constituents, a multifaceted air sampling and monitoring program was implemented. To ensure that potential exposures could be quantified, passive dosimeters, continuous real-time monitoring, time-weighted whole air sampling, and grab samples of vapor clouds were all critical components of the air monitoring program. After the successful completion of the Remedial Action, the pre-Resource Conservation and Recovery Act (RCRA) chemical waste generated from the University's educational and research laboratories was entirely encapsulated and neither on-site workers nor off-site populations were exposed to analyzed compounds above any health-based action level (i.e., 15-min short-term exposure limit [STEL], 8-hr threshold limit value, or time-weighted average permissible exposure limit).     

Porous organoclay composite for the sorption of polycyclic aromatic hydrocarbons and pentachlorophenol from groundwater

Complex mixtures of hazardous chemicals such as polycyclic aromatic hydrocarbons (PAHs) in contaminated soil and groundwater can have severe and long-lasting effects on health. The evidence that these contaminants can cause adverse health effects in animals and humans is rapidly expanding. The frequent and wide-spread occurrence of PAHs in groundwater makes appropriate intervention strategies for their remediation highly desirable. The core objective of this research was to assess the ability of a clay-based composite to sorb and remove toxic contaminants from groundwater at a wood-preserving chemical waste site. Treatment efficiencies were evaluated using either effluent from an oil-water separator (OWS) or a bioreactor (B2). The effluent water from these units was passed through fixed bed columns containing either an organoclay composite or granular activated carbon. The sorbent columns were placed in-line using existing sampling ports at the effluent of the OWS or B2. Individual one-liter samples of treated and untreated effluent were collected in Kimax bottles over the course of 78 h (total of 50 samples). Subsequently each sample was extracted by solid phase extraction methodology, and pentachlorophenol (PCP) and PAH concentrations were quantitated via GC/MS. Columns containing porous organoclay composite, i.e. sand-immobilized cetylpyridinium-exchanged low-pH montmorillonite clay (CP/LPHM), were shown to reduce the contaminant load from the OWS effluent stream by 97%. The concentrations of benzo[a]pyrene (BaP) and PCP were considerably reduced (i.e. >99%). An effluent stream from the bioreactor was also filtered through columns packed with composite or an equivalent amount of GAC. Although the composite reduced the majority of contaminants (including BaP and PCP), it was less effective in diminishing the levels of lower ring versus higher ring PAHs. Conversely, GAC was more effective in removing the lower ring PAHs, except for naphthalene and PCP. The effectiveness of sorption of PCP from the OWS effluent by the composite was confirmed using a PCP-sensitive adult hydra bioassay previously described in our laboratory. The findings of this initial study have delineated differences between CP/LPHM and GAC for groundwater remediation, and suggest that GAC (instead of sand) as the solid support for organoclay may be more effective for the treatment of contaminated groundwater under field conditions than GAC or CP/LPHM alone. Further work is ongoing to confirm this conclusion.     

Biosensor-based diagnostics of contaminated groundwater: assessment and remediation strategy

Shallow groundwater beneath a former airfield site in southern England has been heavily contaminated with a wide range of chlorinated solvents. The feasibility of using bacterial biosensors to complement chemical analysis and enable cost-effective, and focussed sampling has been assessed as part of a site evaluation programme. Five different biosensors, three metabolic (Vibrio fischeri, Pseudomonas fluorescens 10568 and Escherichia coli HB101) and two catabolic (Pseudomonas putida TVA8 and E. coli DH5alpha), were employed to identify areas where the availability and toxicity of pollutants is of most immediate environmental concern. The biosensors used showed different sensitivities to each other and to the groundwater samples tested. There was generally a good agreement with chemical analyses. The potential efficacy of remediation strategies was explored by coupling sample manipulation to biosensor tests. Manipulation involved sparging and charcoal treatment procedures to simulate remediative engineering solutions. Sparging was sufficient at most locations.